LU85356A1 - CONCENTRATED FABRIC SOFTENER COMPOSITION AND METHODS FOR PREPARING THE SAME - Google Patents

Description

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The present invention relates to fabric softener compositions for use in the rinse cycle of a laundering process, and in particular to aqueous concentrated fabric softener compositions which are stable at ambient temperatures low and high, that is to say that these compositions do not form a gel, and which are easily dispersed in water when used.

Compositions containing quaternary ammonium salts having at least one long chain hydrocarbyl group are commonly used for fabric softening when used in the laundry rinse cycle, see, e.g., U.S. Patents.

No. 3,349,033; NO 3,644,203; No. 3,946,115; No. 3,997,453; 15 No. 4,073,735 and No. 4,119,545.

For most aqueous softener compositions containing cationic ammonium compounds | quaternary as active ingredients, the concentration of these cationic compounds has generally been limited to the range of about 3 to 6% by weight (see U.S. Patent No. 3,904,533 and U. S. Patent No. 3,920,565). This low concentration is generally necessary because cationic compounds form gels in aqueous systems at concentrations greater than about 8%, and although the use of electrolytes to decrease the viscosity of these compositions is known ( see in particular US Pat. No. 4,199,545), these electrolytes are far from satisfactory. From a functional point of view, the electrolytes often do not act as desired, in particular to bind concentrations of the cationic compounds close to approximately 12-15%. Furthermore, although the behavior of the electrolytes may somewhat alleviate the problem of gelation, their use is far from satisfactory, since it gives a highly concentrated aqueous system of cationic compounds which does not gel or whose viscosity varies strongly in the usual range of temperatures encountered during its handling, for example 42% at about -18 ° C to about 60 ° C. US Patent No. 3,681,241 describes a concentrated emulsion for softening fabrics , which consists essentially of 3.5 to 6.5 parts; by weight of a compound represented, for example, by distearyl dimethyl ammonium chloride, 3.5 to 6.5 parts by weight of an alkylamido-imidazolinium alkyl sulfate, and 0 to 3 parts by Weight of a different but analogous fatty amido-imidazo-linium alkyl sulfate, said to provide stability at low temperature of the composition. The total active ingredients envisaged are between approximately 8 and 13%.

British application 2053249 A published on February 4, 1981 describes cationic fabric softener compositions containing 15 to 60% by weight of cationic pleating softener, 25 to 75% by weight of an aqueous medium and 0.5 at 40% by weight of a specified water-soluble polymer.

The ü patent. S. No. 3,974,076 describes a fabric softener composition containing quaternary ammonium in concentrations of conventional cationic compounds, i.e., about 3 to about 6%. These compositions are characterized by the very small particle size of the softening compound of the quaternary ammonium type, which is substantially insoluble in water, that is to say that 90% by weight of the quaternary ammonium compounds exist in the form of particles. passing through a 1.2 micrometer filter. The compositions are described as being a combination of the cationic fabric softener, a C 8 alkyl alcohol with about 0.1% "to about 2.0% of a nonionic surfactant having an EHL value (hydrophilic balance-30 lipophilic) from about 8 to about 15, and preferably from about 10 to about 14. Preferred nonionic compounds have a lipophilic hydrocarbyl unit equivalent to 9-15 carbon atoms with 7 to 13. hydrophilic patterns This patent does not refer to the problem of the stability of cationic concentrated aqueous softener compositions, but rather to the improvement of the degree and uniformity of softening by using - 4 '· 3 classic centers.

Each of the patents ü. S. No. 4,076,632; No. 4,157,307 and No. 4,233,164 describes a softener of the quaternary ammonium * type containing inter alia an ethoxy-05 amine "protonated" / but none of them describes salts of the amine and even less salts formed with organic acids of high molecular weight (that is to say higher fatty acids, for example in C2 2 ~ C30 '^ ^ ac ^ - ^ es alkyl-aryl-sulfonic, for example acids ( C 10-108 benzene sulfonic acids; paraffin- (C12-C3Q alkyl) sulfonic acids; olefin-sulfonic acids containing 2 to 30 esters of mono- and di-phosphoric acids Cg-C3Q alcohols comprising the ethoxylates of these alcohols with 1 to 100 moles of ethylene oxide. US Pat. No. 4,118,327 describes a conventional concentration of cationic compound (0.1 to 10%, preferably 1 to 8% by weight) with phosphoric organo-esters as antistatic agents.

The present invention provides aqueous, concentrated softener compositions, stable at low and high temperature, based on softener compounds of the quaternary ammonium type and a lower amount of a salt of a long ethoxylated amine. chain and a long chain organic acid and an electrolyte. Water-soluble polymers such as polyethylene glycol (molecular weight 400, for example) are a preferred preferred ingredient. "

The compositions of the present invention are stable aqueous compositions which contain a high concentration of the cationic fabric softener, which is a water dispersible quaternary ammonium compound, as described below, and an amine salt, also as described below.

The aqueous compositions of the present invention contain at least about 12% cationic softener and up to about 20%, said cationic softener having the general formula I: I · 4 i “ij R + * RNR Y · 05 |

R

wherein the R groups are selected from C 1-6 aliphatic (preferably alkyl or alkenyl), aryl (e.g. phenyl, tolyl, cumyl, etc); aral kyle (for example benzyl, phenethyl, etc.); and their substituted halogen, amido, hydroxy and carboxy derivatives; with the proviso that at least one of the groups R is in C3Q, and preferably in C1 to g, and that the others are lower alkyl groups, and more preferably that at least two groups R are in C1 ^ g and that the others are C1 to alkyl groups (and in particular a methyl or ethyl group), and Y is a water-solubilization anion, for example chloride, bromide, iodide, fluoride, sulfate, methosulfate, nitrite, nitrate, phosphate and carboxy late (i.e. acetate, adipate, propionate, phta-late, benzoate, oleate, etc ...). Representative examples of cationic compounds of formula I include the following: distearyl dimethyl ammonium chloride di-tallow-dimethyl ammonium chloride hexadecyl dimethyl ammonium chloride distearyl dimethyl ammonium bromide di tallow bromide hydrogenated) dimethyl ammonium distearyl chloride, di (isopropyl) ammonium distearyl dimethyl ammonium methosulfate.

The amine salts contemplated in this specification are based on long chain ethoxylated amines and long chain organic acids. The amines are, for example, C12 to C3Q aliphatic amines, and preferably C12 to C2Q amines and mixtures thereof, having reacted with 1 to about 100 moles of ethylene oxide. Amines can

P

! 5 also be reacted with propylene or butylene oxide, then with ethylene oxide. The final oxyalkylated amine must be a water-soluble product. Amines derived from natural fatty acids such as "Armeen" and 05 "Ethomeen" are of particular interest, and they also include mixed alkyl groups ranging from C10 to C18 'OR from C12 & C16' OR from C12 to C15 ΟΏ from C16 to C ^ g, etc ... Preferred ethoxylated amines are those containing from about 5 to about 50 moles of condensed ethylene oxide and those which are preferred are ethoxylated amines having about 10 about 35 moles of condensed ethylene oxide. The most preferred ones contain 12 to 20 moles of ethylene oxide.

The third ingredient is an electrolyte (io-15) in a proportion of about 0.1 to about 1.5% by weight. The use of an electrolyte not only acts to regulate the viscosity, but also promotes stabilization of the system against gelling and phase inversion at high temperatures, for example around 40 ° C. Particularly suitable electrolytes include sodium chlorue and calcium chloride. Other useful electrolytes include sodium formate, sodium nitrite, sodium nitrate, sodium acetate, among others, as well as the water-soluble salts of other cations such as potassium, lithium, magnesium, ammonium, etc ...

Secondary amounts of lower alkanols can be used, particularly when it is desired to further modify the viscosity. In general, alcohols tend to reduce viscosity at room temperature, although moderate amounts can produce a lowering of the phase inversion temperature. The preferred compositions of the present invention exhibit phase inversion temperatures above about 80 ° C, and preferably above about 90 ° C, with amounts of alcohols from about 1 to about 10% by weight.

Particularly preferred alcohols are ethyl alcohol and isopropyl alcohol.

In addition to the above components of the fabric softener compositions of the present invention, there can also be incorporated many conventional additional and optional ingredients which do not adversely affect the stability or functional characteristics of the compositions of the invention. Thus, for example, it is possible to incorporate common ingredients such as perfumes, dyes, pigments, opacifiers, germicides, optical brightening agents, anti-corrosion agents (for example sodium silicate), water-soluble polymers, antistatic agents, etc. .. When used, each of them can constitute 0.01% to about 5% by weight of the composition.

It is naturally obvious that the most available chemical materials and in particular those containing a hydrocarbyl unit are generally mixtures of closely related units. Thus, the long chain alkyl substituents (R) of the cationic compounds used in the present invention can not only be constituted by a single long carbon chain, but more probably by a mixture. In this regard, a particularly useful quaternary group in which the alkyl groups originate from tallow may contain about 35% C ^g and 60% C ^g and minor amounts of C,. and even others.

The fabric softener compositions of the present invention must have, in addition to viscosity and phase stability, the required viscosity (i.e., pourability) and water dispersibility in the cycle rinse (or any other form of dilution before use) requested by consumers who have grown accustomed to accepting and even demanding less concentrated products. Thus, the products contemplated in this specification can have viscosities between about 30 and about 250 mPa.s and preferably between about 40 and about 120'mPa.s. | 7

In addition to allowing excellent characteristics of dispersibility in water, the amine salts used contribute to softening so that, for example, a concentrate of 12% of quaternary compound and 05 2% of amine salt is not just twice a composition containing 6% of the conventional cationic compound, but is almost 2-5 times as effective.

The general procedures for preparing the present composition are numerous, the final product varying somewhat in terms of its stability. The procedure chosen depends on the components used and differs in the order of addition of the materials and the operating conditions.

A generally preferred procedure (A) is to add the nonionic material and the colorant, if used, to the weight of the formulation water which is at about 70 ° C. The solution is added slowly to this solution. cationic softener in "melted" form (50-60 ° C) to which the amine salt has already been added. It generally forms a gel. The mixture is cooled to about 40 ° C and then the electrolyte is added to break the gel. The composition is then cooled to room temperature with stirring. An alternative to procedure (A) is to adjust the pH to about 12 before the addition of the molten ca-25 compound. In this case, no gel is formed.

After cooling to about 40 ° C, the pH is readjusted to 5-6, cooled with stirring to room temperature, then the electrolyte is used to adjust the viscosity (procedure B). Another still procedure (C) consists in adding the nonionic compound and the electrolyte to at least 80% of hot water (approximately 40 ° C.), then the cationic softener and the salt. amine as in procedure (A). In general, it does not form gel.

The remainder (if any) of water is then added, and the composition is then cooled with stirring to room temperature.

The following examples illustrate the present in-.

ï '* 8 vention without limiting it. The parts are expressed by weight unless otherwise specified.

EXAMPLE 1

Following the procedure (A) described above, 1 part of polyethylene glycol (molecular weight 400) is dissolved in 1.2 parts of 0.2% dye solution in approximately 70 parts of water at a temperature of approximately 70 ° C. 17.6 parts of distearyl dimethyl ammonium chloride (active 10 to 75% and containing approximately 10% of isopropanol, the remainder being water) are slowly added to this solution. molten form, to which 3.7 parts of Ethomeen T25 (tallow amine (40% C,,; 60% C, 0) condensed with 15 moles of oxy-lo of ethylene) have previously been added and 1.3 parts of dodecyl-benzene-sul-15-fonic acid (temperature = 55 ° C.) with stirring. A gel forms. The gel is cooled to about 40 ° C, then 0.5 part of calcium chloride dihydrate is added. The mixture is cooled to room temperature (about 20 ° C) while stirring. A stable product is obtained having a viscosity of about 100 mPa.s.

EXAMPLE 2

The procedure of Example 1 is repeated using the following parts of (A) cationic compound (active), (B) amine, (C) sulfonic acid and (D) electro-lyte.

(a) A = 12; B = 1.0; C = 0.32; D - 0.5 (b) A = 14; B = 1.5; C = 0.52; D »0.5 (c) A = 16, · B = 1.8; C = 0.63; D = 0.7 (d) A = 18; B = 2.5 d C = 0.88; D = 1-rO.

30 EXAMPLE 3

Examples 1 and 2 are repeated, using the following compounds in place of distearyl dimethyl ammonium chloride: (a) di-tallow-dimethyl ammonium chloride (b) distearyl dimethyl ammonium methosulfate (c) di bromide (hydrogenated tallow) dimethÿl-ammonium

(d) dihexadecyl-dimethyl-ammonium chloride I

9 (e) distearyl diethyl ammonium chloride EXAMPLE 4

Examples 1, 2 and 3 are repeated, in all cases adding 1 part of polyethylene glycol (molecular weight 400) with the amine salt in the first step of the preparation process.

Polyethylene glycol (molecular weight 400) is representative of the water-soluble low molecular weight polymers which can optionally be used in the fabric softener compositions of the present invention.

Among other useful polymers, reference may be made to the aforementioned published British patent application No. 2,053,249 A which is cited by way of reference in the present specification. The compositions of the present invention may contain any or all of such polymers as well as other water-soluble polymers. In the compositions of the present invention, 0.1% to 20% by weight of these materials can be used, relative to the weight of the total composition.

20 EXAMPLE 5

Each of Examples 1 to 4 is repeated above using the following compounds as electrolyte: (a) sodium chloride (b) sodium nitrate (c) sodium formate (d) ammonium bromide (e) sodium chloride potassium (f) calcium nitrate (g) lithium acetate 30 (h) magnesium chloride. ~ EXAMPLE 6

Each of Examples 1 to 5 is repeated, as regards the composition, but following the procedure (B) to prepare the compositions. In this procedure, the change in procedure described in Example 1 is to adjust the pH to 12 with sodium hydroxide after dissolving the amine salt (and polyethylene glycol 10 if used ), and readjust the pH to 5-6 with hydrochloric acid after the addition of the cationic compound.

In this case, a gel does not form as in procedure (A). The electrolyte is added after cooling the mixture to room temperature.

EXAMPLE 7

Each of Examples 1 to 5 is repeated, as for; the composition, but following the procedure (C) to prepare the compositions.

In this process, the amine salt (and water-soluble polyethylene glycol if used) is dissolved in 80% of the weight of water in the formulation at a temperature of 35-40 ° C. then add the electrolyte, then the molten cationic compound. The remainder of the weight of the formulation water is then added and the mixture is cooled to room temperature with stirring.

EXAMPLE 8

Following the procedure (A) described above, 1 part of polyethylene glycol (molecular weight 400) and 1.2 parts of 0.2% solution of dye are dissolved in approximately 70 parts of water at a temperature around 70 ° C.

• 17.6 parts of di-tallow-dimethyl-ammonium chloride (75% dlac-25 tivité and containing approximately 10% isopropanol, the remainder being water) are slowly added to this solution in the molten form to which previously added 2 parts of Ethomeen T 25 / tallow amine (40% --- “of C ^ g, 60% of Cl8) condensed with 15 moles of ethylene oxide / and 0.62 part of stearic acid (temperature of 55PC) 30. shaking. A stable product is obtained having a cosited screw of approximately 100 mPa.s.

EXAMPLE 9

The operations of Example 8 are repeated, using the portions of cationic compound, of amine and elec-trolytes of Example 2, and at the same time varying the amount of stearic acid so that it is stoichiometric with respect to the amount of amine.

11 EXAMPLE 10

The operations of Example 9 are repeated, replacing the stearic acid with a stoichiometric amount. as the following acids: lauric / cis-9-dodecenoxque, 05 myristic, cxs-9-tetradecenoxic, pentadecanoic, cis-9-pentadecenoic, palmitic, cis-9-hexadicenoic, hepta-decanoic, cis-9-heptadecenoxic, oleic, linoleic, linolenic / Jt-eléostéarique, 4-oxo-cis-9- trans-11, trans-13-octadëcatriénoxque, ricinoleic, dihydroxystéarique, 10 nonadëcanoxque, eicosanoïque, cis-ll-eicosénoxque, cis-9-eicosénoquequeque, eicosénoïquequeque , arachidonic, eicosapentanenoic, docosanoxque, cis-13Adocosian-noic, docosadxenoxic, docosatetranoic, 4,8,12,15,19-docosapentanenoxic, docosahexanoic, tetracosanoxque, 15 tetracosenoic, 4,8,12a15,18,18 their mixtures.

EXAMPLE 11

Each of Examples 9 and 10 is repeated, replacing the quaternary compound on the one hand with those of Example 20 and on the other hand repeating all these examples using, in the composition, 1 part of polyethylene glycol -col (molecular weight 400).

The aqueous softener compositions of the present invention are generally applicable like other compositions of this type, useful in particular in the rinse cycle of an automatic washing machine. In these operations as well as in any other method of clothing treatment, the compositions are usually used so as to generally obtain an active concentration of about 0.005% to 0.3% based on the weight of the treated clothing. , preferably from 0.007% to about 0.2%, and more preferably from 0.01% to about 0.15%. -

Claims (10)

12 CLAIMS - 1. Concentrated, aqueous, stable fabric softener composition, characterized in that it comprises (A) 12 to 20% by weight of a cationic softener of formula: 05 El ^ \ + '**> *** ^ '8 I4 10 wherein Rlf R2, R3 and R4 are C1 to C3Q aliphatic radicals, at least two being C ^^ to C3Q alkyl groups; (B) 1 to 5% by weight of an amine salt and 15 (C) 0.5 to about 5% by weight of an electrolyte. 2. Composition according to claim 1, characterized in that the compound (A) is disté-aryl-dimethyl-ammonium chloride. 3. A composition according to claim 2, charac-20 in that the amine salt is the reaction product of a nonionic ethoxylated amine containing an average of about 15 moles of ethylene oxide and a acid. 4. Composition according to claim 1, characterized in that the ratio of (A) to (B) is approximately 25 40: 1 to 2: 1. 5. Composition according to claim 4, characterized eïT'ce that the amount of compound (A) is about 12% and that of the compound (B) is about 2%. 6. Composition according to claim 1, characterized in that the total concentration of the softener is about 12 to 15% by weight. 7. Process for the preparation of a composition according to claim 1, characterized in that it consists first of all in preparing an aqueous solution of the amine salt in hot water at a temperature reaching about 80 ° C, then add the cationic softener in molten form to form a gel, cooling said gel below 40 ° C.,. 13 "# s then add an electrolyte to break the gel. 8. Method according to claim 7, characterized in that the temperature of the hot water is approximately 70 ° C, the gel is cooled to a temperature immediately below 40 ° C and / when the gel is broken, the mixture is cooled to room temperature with stirring. 9. Process for the preparation of a composition according to claim 1, characterized in that it consists first of all in preparing an aqueous solution of the amine salt in hot water at a temperature reaching about 80 ° C, to adjust the pH with an alkaline material to a value greater than about 10, to add the cationic softener in the molten state, to readjust the pH to less than 7, to cool to about room temperature, then to add - 15 ter the electrolyte to adjust the viscosity. 10. Process for the preparation of a composition according to claim 1, characterized in that it consists first of all in preparing an aqueous solution of amine salt, then in adding the electrolyte then the cationic softener in the form melted and cooled to room temperature. l · »i i) i